JPH0367145B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present application relates to a new fiber treatment agent and textile products, and in particular to a treatment agent suitable for keratinous fibers such as wool, and a treatment agent that provides excellent durability and flexibility. The purpose of the present invention is to provide textile products with the following properties. (Prior Art) In order to prevent undesirable shrinkage and felting that occur during washing of textile products made of keratinous fibers, methods using various silicone-based treatment agents have been proposed. That is, a method using a composition consisting of a catalyst and an organic solvent solution containing a linear polysiloxane having a hydroxyl group at the end and having a viscosity of at least 50 cS and a methylhydrodiene polysiloxane (see Japanese Patent Publication No. 33435/1983). ), a method using a solution of high molecular weight polysiloxane and a catalyst in a chlorinated solvent (Japanese Patent Publication No. 1973-
38036), a method of treatment with a diorganopolysiloxane composition containing an amino group and an alkoxy group (see Japanese Patent Publication No. 53-28468), a composition of an organopolysiloxane containing a mercapto group and an amino group Method of processing (Special Public Interest Publication 1983-
(See Publication No. 4114) have been proposed. but,
Although both of them show the effect of preventing shrinkage of keratinous fibers during washing, the effect is insufficient, and
There is also the disadvantage that the texture of treated textile products is impaired, and the reality is that no shrink-proofing softening agent with sufficient washing durability and a treatment method using the same have yet been completed. (Structure of the Invention) The fiber treatment agent of the present invention imparts highly durable shrink-proofing properties and flexibility to textile products, especially textile products containing keratinous fibers, which is characterized by (A) (1) 100 parts by weight of organopolysiloxane having at least two hydroxyl groups bonded to silicon atoms in one molecule, (2) 0.3 to 20 parts by weight of anionic emulsifier, 25 to 600 parts by weight of water, (B) Above (A) For 100 parts by weight of the organopolysiloxane (1), (1) 0.1 to 10 parts by weight of a reaction product of an amino-functional silane or its hydrolyzate and an acid anhydride, and (2) 1 to 50 parts by weight of colloidal silica. 1 to 60 parts by weight of a homogeneous dispersion of (C) an epoxy-functional alkoxysilane per 100 parts by weight of the organopolysiloxane of (A)(1) above;
and (D) 0.01 to 10 parts by weight of a curing catalyst per 100 parts by weight of the organopolysiloxane of (A)(1) above. Hereinafter, the composition of the fiber treatment agent of the present invention will be explained in detail. First, it is convenient that component (A) in the treatment composition of the present invention is in the form of an aqueous silicone emulsion. The organopolysiloxane constituting component (A) must have at least two hydroxyl groups bonded to a silicon atom in one molecule. Organic groups other than groups, molecular structure,
There are no particular limitations on the degree of polymerization, etc., and various conventionally known ones can be used. In addition, in the present invention, the siloxane preferably has a molecular weight of 10,000 or more,
This is not necessarily a limitation. Such organopolysiloxanes can be obtained by, for example, using a ring-opening reaction method with a cyclic siloxane such as octaylorganocyclotetrasiloxane, or by using a linear or branched organopolysiloxane having a hydrolyzable group such as an alkoxy group or an acyloxy group. Method of hydrolyzing organohalogenosilane 1
It can be synthesized by a method of hydrolyzing one species or two or more species. In addition, the anionic emulsifier used in the preparation of component (A) is a conventionally known one, preferably sulfonic acids, sulfuric esters, phosphoric esters, or salts thereof, which have a surface-active action that can serve as an emulsion polymerization catalyst. Specifically, aliphatic sulfate ester salts such as sodium lauryl sulfate, benzenesulfonic acids substituted with aliphatic hydrocarbon groups such as dodecylbenzenesulfonic acid, naphthalene sulfonic acids substituted with aliphatic hydrocarbon groups, polyethylene glycol sulfate ester salts, and lauryl. Examples include phosphates. This aqueous silicone emulsion as component (A) can be prepared by employing various conventionally known methods. A method of emulsifying an organopolysiloxane and water in the presence of an anionic emulsifier, or a method of emulsifying a cyclic siloxane such as octoorganocyclotetrasiloxane and water using an anionic emulsifier, and then using a conventionally known method. Examples include a method in which a ring polymerization catalyst is added and polymerized under heating to synthesize an organopolysiloxane having two or more Si--OH bonds in one molecule and to obtain the desired aqueous emulsion. In this case, a trifunctional silane represented by RSi(OR') ₃ (where R is an alkyl group, alkenyl group, aryl group, etc., R' is an alkyl group, acyl group, etc.) is added to the cyclic organopolysiloxane. Alternatively, the trifunctional silane may be separately emulsified and added to the cyclic siloxane emulsion. The amount of anionic emulsifier used in the preparation of component (A) is in the range of 0.3 to 20 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the organopolysiloxane. This is because if the amount used is less than 0.3 parts by weight, emulsification becomes difficult and it is difficult to obtain the desired aqueous emulsion, whereas if it exceeds 20 parts by weight, the final film obtained becomes weak. The amount of water to be used is not particularly limited as long as it can form an aqueous emulsion, but generally it is about 25 to 600 parts by weight per 100 parts by weight of organopolysiloxane. be done. In addition, when preparing the above-mentioned aqueous emulsion, the use of nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, or fluorine-based emulsifiers is a treatment of the present invention. It is optional as long as it does not significantly reduce the properties of the agent. Next, component (B) in the treatment agent of the present invention is used for the purpose of improving the rubber physical properties of the elastomer film obtained from the treatment agent composition of the present invention and the adhesion (adhesion or fixation) to the fiber that is the base material. These are the ingredients to be mixed. One of the components constituting component (B) is a reaction product of an amino-functional silane or its hydrolyzate and an acid anhydride, and an amino-functional silane that can be used in the synthesis of this reaction product. For example, the formula YR ¹ _n Si(OR ² ) _3-n [wherein Y is a 2-aminoethyl group, a 3-aminopropyl group, a N-(2-aminoethyl)-3-aminopropyl group, etc.] R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ² is a lower alkyl group, and m is 0, 1 or 2. ], specifically 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-
Aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2
-aminoethyl)-3-aminopropyltrimethoxysilane, N-triethylenediaminepropyltrimethoxysilane, N-triethylenediaminepropylmethyldimethoxysilane, etc., and (partial) hydrolysates of these are also used in the present invention. can do. Examples of acid anhydrides include methyltetrahydrophthalic anhydride, methylhymic anhydride, benzophenonetetracarboxylic anhydride, phthalic anhydride, ethylene glycol bistrimelitate, maleic anhydride, and pyromellitic anhydride. succinic anhydride, polyazelite polyanhydride, trimellitic anhydride, nadic anhydride, phenylmaleic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, dodecylsuccinic anhydride , dichloromaleic anhydride, chlorendic acid anhydride, and the like. In the reaction between the amino-functional silane and the acid anhydride described above, the desired product can be easily obtained by simply mixing the two at room temperature (exothermic reaction). The reaction molar ratio of the amino-functional silane or its hydrolyzate and the acid anhydride may be equimolar, but there is no problem if either one is used in excess. There are no restrictions on the type of colloidal silica, but examples include those with a particle size of 10 to 40 μm and stabilized with sodium or aluminum ions. It can be easily obtained as Snowtex 40 etc.). Here, the usage ratio of colloidal silica and reaction product is 0.1 to 10 parts by weight per 1 to 50 parts by weight of colloidal silica, preferably 0.1 to 10 parts by weight per 100 parts by weight of solid content of colloidal silica. It is preferable to use the reaction product in an amount of 1 to 5 parts by weight. This is because if the amount of the reaction product used is too small, the effect of improving adhesion to the substrate will be small, whereas if it is too large, the fluidity of the composition will decrease. Component (B) is prepared by gradually dropping the reaction product into a desired amount of colloidal silica at room temperature while stirring. The reaction product of the amino-functional silane or its hydrolyzate and the acid anhydride in component (B) has the effect of improving the adhesion of the elastomer obtained from the treatment composition of the present invention to the base material. In addition to this, it also has the effect of enhancing the reinforcing properties of colloidal silica against the organopolysiloxane in component (A). Here, the usage ratio of component (A) and component (B) is
(A) Organopolysiloxane 100 contained in component
The amount of component (B) is 1 to 60 parts by weight, but
The amount is preferably 2 to 30 parts by weight. This is because if the amount of component (B) blended is too small, the strength of the resulting elastomer film will be insufficient for the purpose, and if it is too large, the hardness of the elastomer film will increase and the treated textile product will become soft. This is considered to be within the above range because the bond becomes hard. Next, the epoxy-functional alkoxysilane, which is component (C) in the treatment agent of the present invention, is a component that is blended in order to improve the adhesion of the elastomer film obtained from the treatment agent composition of the present invention to the fiber that is the base material. For example, the formula, ^ZR3oSi ( ^OR4 ) _3-o [wherein Z is a glycidoxypropyl group or a β-(3,4 _- epoxycyclohexyl)ethyl group, and ^R3 is a carbon number of 1 to 6 monovalent hydrocarbon group, R ⁴ is a lower alkyl group, n is 0, 1 or 2], specifically γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, Sidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane
-epoxycyclohexyl)ethylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and the like. If the amount of component (C) is too low, the adhesion of the elastomer film obtained from the treatment composition to the fibers will be poor, and if it is too high, the film will be hard.
Based on 100 parts by weight of the organopolysiloxane component
The range is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight.
The range is in parts by weight. These epoxy-functional alkoxysilanes are (B)
At any stage during the preparation of the ingredients, after uniformly mixing both components (A) and (B), and even after uniformly mixing both components (A) and (B) with component (D) described below. can also be blended. The curing catalyst as component (D) is used to cure the treatment composition according to the present invention, and includes, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, octylic acid Examples include metal salts of organic acids such as tin, tin laurate, iron octylate, and lead octylate, titanate esters such as tetrabutyl titanate, and amine compounds such as n-hexylamine and guanidine. In addition, before using these curing catalysts, O/W using an emulsifier and water in a conventional manner.
It is preferable to form a mold emulsion. The curing catalyst is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the siloxane in component (A), but this is 0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight.
If less than 10 parts by weight is used, the composition according to the present invention cannot be cured to a sufficiently satisfactory degree, and even if 10 parts by weight or more is used, no particular effect is observed on the curing reaction, and the heat resistance of the resulting elastomer is deteriorated. This is because it tends to have a negative effect on sexuality. When preparing the processing agent composition according to the present invention,
It is essential to homogeneously knead component (B) colloidal silica and the reaction product in advance. The most preferable mixing order is to prepare a silicone aqueous emulsion, which is component (A), and then mix component (B) which has been homogenized in advance, and then mix component (D). It is sufficient to carry out the mixing using a conventional stirring device. Component (A), component (B)-(2) (colloidal silica)
If component (B)-(1) (reaction product) is added to a mixture of components (D) and (D), a gel-like substance will be produced, and if such a mixing method is adopted, no stirring will be necessary. Even if you do this, it cannot be dissolved uniformly. In the processing agent composition according to the present invention, the pH is 3.
~12, preferably in the range of 5 to 9. This is because if the PH is outside the above range, there will be various problems in handling at the beginning of work, and worker safety should be taken into consideration. Then, a pH range of 6 to 9 is preferred. This PH adjustment can be performed at various PH values depending on the PH value of the composition.
Modifiers can be used, such as, for example, sodium carbonate. The processing agent composition of the present invention includes components that are usually added to water-based paints, such as thickeners, antifoaming agents, pigments, dyes, preservatives, penetrants (ammonia, etc.), and various antistatic agents (anionic, etc.). , nonionic) may be optionally added. In order to obtain desirable shrink resistance and flexibility with durability (washing resistance), the solids content of the treatment agent of the present invention should be 0.5 to 10% by weight for textile products, for example textile products containing keratinous fibers. Attach it so that
It is preferable to allow reaction and fixation. The treatment agent of the present invention is applied to textile products, and the reaction and
For fixing, a padding method or a coating method can be used. In the case of the padding method, first, the treatment agent of the present invention is made into an aqueous solution of about 2 to 40% by weight, impregnated into the target textile product in a padding tank, the amount of adhesion is adjusted by centrifugation or mangle rolls, etc., and then the treatment agent is prepared in a drying oven. Alternatively, drying and further heat treatment are performed using fiber processing equipment such as a pin tenter. At that time, it is usually heated for 30 seconds to 30 seconds at 100 to 120℃.
After drying for a minute, heat treatment is performed to react and fix the solid content.
The heat treatment is preferably performed at 140 to 160°C for 1 to 10 minutes, more preferably 1 to 3 minutes at 140 to 160°C. In addition, in the case of a coating method, for example, CMC, methylcellulose, sodium polyacrylate, etc. are added to the treatment agent of the present invention to thicken it, and the target textile product is coated using a roll coater, knife coater, etc. , drying and heat treatment are performed under the same conditions as the padding method described above. The required heat treatment conditions are the same as for the padding method. The textile product of the present invention is characterized by being treated with the treatment agent according to claim 1. Among these, the effect is remarkable when this textile product contains keratinous fibers. Here, textile products containing this keratinous fiber include, for example, lamb's wool, botanical wool, mohair,
It includes products of fibers that have a scale-like structure on the fiber surface, which are classified as animal hair including so-called wool, such as cashmere and alpaca wool, and blended products of these and other fibers, and also include twisted yarn, The treatment agent of the present invention is effective regardless of the type of keratin fiber and the form of the product, including any form of knitted fabric, woven fabric, or finished garment. When a textile product containing keratinous fibers is treated with the treatment agent of the present invention, a treated product having both excellent shrink-proofing properties and flexibility can be obtained, and the fibers can also be bonded to each other during wear. It is also possible to prevent pilling caused by entanglement, and these properties are durable and do not deteriorate even after repeated washing. That is,
The treated textile products of the present invention do not shrink or become felt when washed, and retain their original size and texture immediately after treatment. Furthermore, this treated textile product does not shrink even when washed in a water-based household using an electric washing machine, and becomes washable wool. The fiber treatment agent of the present invention is effective for general natural and synthetic fiber products, but is particularly effective for keratinous fibers. Furthermore, the treatment agent of the present invention can be used for keratinous fibers other than clothing, such as hair, for the purpose of preventing stiffness and shaping by film coating. Next, examples of the present invention will be given. Example 1 (A) Component (parts indicate parts by weight. The same applies hereinafter) 500 parts of octamethylcyclotetrasiloxane,
25 parts of methyltrimethoxysilane, 465 parts of water, and 10 parts of dodecylbenzenesulfonic acid were emulsified using a homomixer, and then passed through a homogenizer twice at a pressure of 300 psi to obtain a stable emulsion.
This was placed in a flask and heated at 70°C for 12 hours.
The mixture was then cooled to room temperature, left for 24 hours, and then adjusted to pH 7.0 using sodium carbonate. The non-volatile content of this is 47% and 20% of the organopolysiloxane separated using methanol.
The viscosity of the toluene solution was 7200 cP (25°C). Component (B) 221 parts of 3-aminopropyltriethoxysilane was added dropwise to a mixture of 98 parts of maleic anhydride and 319 parts of ethanol at room temperature and stirred to obtain a reaction product. Colloidal silica (manufactured by Nissan Chemical Co., Ltd., Snowtex 40, active ingredient 40%, _Na2O amount 0.6%, PH9.3)
When 30 parts of the reaction product obtained above was gradually added dropwise to 1000 parts at room temperature while stirring, a translucent homogeneous dispersion was obtained. The pH of this product was 3.4. (D) Ingredients 30 parts of dioctyltin dilaurate, 1 part of polyoxyethylene nonyl phenyl ether and 69 parts of water
The mixture was emulsified using a conventional method. Emulsion composition Next, 100 parts of component (A), 9 parts of component (B) and component (D)
After uniformly mixing 1.5 parts, add γ-glycidoxypropyltrimethoxysilane as component (C).
0.5 part was added and further uniformly dissolved to obtain a silicone aqueous emulsion composition. This is also an emulsion. This emulsion composition contained 41% curable solids and had a pH of 6.8. Comparative Example 1 An emulsion composition was prepared in the same manner as in Example 1 except that the component (C), γ-glycidoxypropyltrimethoxysilane, was not used. This is called an emulsion. The hardening solid content of emulsion is
The percentage was 40.8%, and the pH was 6.8. Comparative Example 2 N-(2-
7.5 g of (aminoethyl)-3-aminopropylmethyldimethoxysilane and 1000 g of dimethylpolysiloxane, which has a viscosity of 3000 cS at 25°C and whose molecular chain ends are both blocked with hydroxyl groups, were charged and heated at 150°C for 2 hours in a nitrogen atmosphere. By heating and stirring, both ends of the molecular chain are converted to N-(2-aminoethyl)-
A polymer capped with 3-aminopropylmethylmethoxysilyl groups was obtained. The viscosity of this polymer is
It was 5500cS (25℃). Next, 350 g of the polymer obtained above, 40 g of a polyoxyethylene alkyl ether type nonionic surfactant, and 610 g of water were mixed into a homomixer to obtain an emulsion. Next, by the same method, the molecular chain end was blocked with trimethylsilyl group, and the viscosity at 25℃ was 30cS.
350g of methylhydrodiene polysiloxane,
An emulsion consisting of 40 g of polyoxyethylene alkyl ether and 610 g of water was obtained. These emulsions were used to prepare treatment solutions as shown in Table 1, and wool tropical cloth was padded. After adjusting the wet pick-up to 100% using a mangle roll, the emulsions were heated at 100°C in a hot air dryer. Dry for 2 minutes and further dry at 160℃/2
A treated cloth was obtained by heating and curing for several minutes. The treated fabric was washed 20 times in a household washing machine according to JIS L-217103 method, and the shrinkage rate and texture were evaluated during and after washing. The result is the first
Also listed in the table. In the table, the blending amount of the treatment liquid is in parts by weight, and the component D emulsion is the same as that used in Example 1. (Same below)

【table】

[Table] The shrinkage rate can be calculated by attaching marked lines at 10 cm intervals vertically and horizontally on the treated fabric in advance, measuring the distance between the vertical and horizontal marking lines after drying after each washing cycle, and using the following formula. It is expressed as the total value of the vertical and horizontal shrinkage rates. Vertical or horizontal shrinkage rate (%) = 10-l/10x100 In the above formula, l is the measured value of the gauge line interval after washing (cm)
It is. Texture was evaluated using the following four grades. ◎ Soft and has excellent slippery feeling 〇 Good △ Slightly good × Texture Rough and hard with no slippery feeling Next, the wool knit cloth was treated with the above-mentioned wool tropical cloth using a treatment solution containing emulsion ~ as shown in Table 2. Treat as if
Furthermore, in the same way, using a household electric washing machine, JIS
It was washed according to the L-217103 method and the shrinkage rate and texture were evaluated. The results are also listed in Table 2, and it was found that even after washing, the treatment agent of the present invention did not shrink much and retained its texture, similar to the results shown in Table 1. .

【table】

Claims (1)

[Scope of Claims] 1 (A) (1) 100 parts by weight of an organopolysiloxane having at least two hydroxyl groups bonded to silicon atoms in one molecule, (2) 0.3 to 20 parts by weight of an anionic emulsifier, ( 3) Water 25 to 600 parts by weight, (B) Per 100 parts by weight of the organopolysiloxane in (A)(1) above (1) Reaction product of amino-functional silane or its hydrolyzate and acid anhydride 0.1 (2) 1 to 60 parts by weight of colloidal silica; silane
and (D) a curing catalyst comprising 0.01 to 10 parts by weight per 100 parts by weight of the organopolysiloxane of (A)(1) above. 2. A textile product treated with the textile treatment agent according to claim 1. 3. The textile product according to claim 2, wherein the fibers are keratinous fibers.